Phosphonic diamides



"saturated or' unsaturated.

United States Pate'fit'f) PHOSPHONIC I DIAMIDES James N. Short, Berger,Tex., assignor to Phillips Petroleum Company, a corporation of DelawareNo'nmwin Application April 26, 1954 Serial No. 425,770

21" claims; cl."26o sti This invention relates to phosphonic diamides.In one aspect this invention relates to alkapolyenephosphonic diamidesas new compounds. In another aspect this 1nvention relates 'to'alkenynephosphonic diamides. In another aspect this invention relates toalkapolyynephosphonic diamides. In another aspect this invention relates"to reacting a haloalkeneph'osphonicdihalide containing at ..least oneethyleniclinkage with an amine containing at ,least one hydrogen atomattached to-the 'nitrogen atom.

l-n still another aspectthis invention relates to polymers of the saidphosphonic diamides. Instillanother aspect this invention relates to newchemical compounds-represented by the structural-formulas-given anddefined below.

Further according to'the invention there are provided as new compoundsphosphonic diamides represented by I the structural formula .wherein Ais a membcr selected -from- 'a group consisting of unsubstituted andhalogen-substituted alkapolyene,

alkenyne and alkapolyyne hydrocarbon radicals, and a five to sixmembered ring' containirigat least one of said unsubstituted orhalogen-substituted hydrocarbon radicals; R' is amembercontainingfrom-zero to-ten-carbon atoms selected from the group consisting ofhydrogen, hydro- "eatersend heterocycli'c radicals, said hydrocarbonradi-' cals being selected from the group consisting of aromatic,

i satu' ratejd and unsaturated acyclic, and" saturated and unsa uratedalic'yfclic' radicals, and cornbinationsbflthe radicals 'a's' defined byR; andwheregin addition, two

R radicals together with the nitrogen aftach'ednhere'to can form aheterocyclic ring containing from five to seven atoms, at least three ofwhich are carbon, the remainder being selected from the group consistingof carbon, nitrogen, si'ilfu'r'a'n'd oxygen. The heterocyclicrad icalcan be Throii'lioiit the specification and in the clai'msz t'liefter'fi'i alke'ne means a hydrocarbon radical containing at least onee'tliylenic linkage; the term alkapolyene means a "hydroc'a'rbo'n'radical containing at least two ethylenic 6 Nov"):

2,818,406 latented Dec. 31, 1957 "ice "R--GEO'CEC-P N RI/I VI )2 where R"""is' as 'defined" above. R, R and R" are selected from the groupconsisting of hydrogen; halogen; and unsubstituted and:halogen-substituted hydrocarbon radicals,

"said radicals being selected from the group consisting of "aromatic,saturated a'ndunsaturated acyclic, and saturated and unsaturated'alicyclic radicals, and combinations of these radicals, and wherein R, Rand R can'be the same "or' 'different." In addition, in the case ofFormula'sl, III, lV' andV'and R and R together with the-four-carbon Thesum of all-the 'It is to{ be noted thatthe phosphoniddiam'ides of 'theinvention are characterized" by either an alkapol'yiene grouping, an-alkenyne grouping, an alkapolyyne group- Included in the group ofcompounds repre'sented by' the above formulas are:N,N,N',N-tetraallyl-1,3 butadienel pllosph'oni'c diamide,N,N,N',N-tetraallyl-l,3'butadiene- -2 =phosphonic diamide,N,N,N',N-tetracyclohexenyl-2,3- dimthyl-LB-butadiene l phosphonicdiamide, 'N,N',N",N'- tetra -'p*--'2v-"butenylphenyl -4 phenyl 1,3butadie'n'el-phosphonic diamide,N,N,N,N-tetracinnamyl-1,3-cyclohexadiene-l-phosphonic diamide,N,N,N,N'-tetraa1lyl- 3-buten-1-yne-1-phosphonic diamide,N,N,N',N'-tetraallyl-l-butene-3-yne-l-phosphonic diamide, N,N'-dially1--1,3-cyclopentadiene-l--phosphonic diamide, N,N'--dii- 2- quinolyllj-hexadiene-l--phosphonic diamide, 1,3-hexadiene-Z-phosphonicdipiperazide, 1,3,7-tetradecatriene-lphosphonic 'dirnorpholide,N-,N,N',Nrtetraphenylt-(p- 'tert-butylphenyl)- 1',3 butadie'ne-lphosphonic diamide, N,N,N,N'-tetramethyl 1 ,3-butadiene-lrphosphonic'diamide, N,N,N,N tetramethyl-1,3-butadiene-2-phosphonic diamide,1,3-butadiene-l-phosphonic'diamide, 1,3-hexa'dione-lephosphonic diamide,N,N-,N,N'-tetramethyl-3-bu- 2-chloro-1 3-butadiene-1'-phosphonicdiamide,. N,N uallylbenzyl-3-he en l-yne-2-phosphonic diamide, N,Nbis(4*-phenylbuty1)-3,5 hexadien -l-yne -'l -phosphonic diamide, N,N,N,N'-tetracyclohexyl-1,3-pentadiyne1 l phosphonic diamide, N,N'-bis(2-napht-hyl)-2bromo 1:,3-butadiene l-phosphonic diamideandN,N,N,N"-tetra-(.decyl')- 7-octen-l,3-diyne-l-phosphonic diamide.

Further, according to the invention, there arepro'vidednewcompositionsof; mattercompr-ising polymers ofi the pholine.

novel phosphonic diamides represented by the above structural formulas.

Still further according to the invention, there is provided a method ofpreparing the phosphonic diamides represented by the above structuralformulas.

A preferred method of preparing these new unsaturated hydrocarbonphosphonic diamides is by reacting under anhydrous conditions ahaloalkene-phosphonic dihalide containing at least one olefinic doublebond with an amine containing at least one hydrogen attached to thenitrogen atom or with ammonia in an amount in excess of thestoichiometric quantity needed. When employing strongly basic amines thereaction is believed to proceed according to the following equation:

N(R')2 where R, R, R", and R are groups as defined above, and X iseither C1 or Br.

It is desirable to use at least 4 mols of amine to one mol ofhaloalkenephosphonic dihalide to bring about complete amidation, plus anadditional mol of amine for each chlorine which is attached to carbonand which is to be removed by dehydrohalogenation. When a relativelyweak amine is employed the dehydrohalogenation may not occursimultaneously with the amide formation. In such instances, if it isdesired to dehydrohalogenate it will be necessary to treat the amidewith a relatively strong base in a subsequent step.

One method of operation is to add the haloalkenephosphonic dihalide,with constant stirring. to an excess of the amine, either undiluted ordiluted with a suitable solvent. The reaction is usually eifected at atemperature in the range between and 70 C., preferably between 40 and 50C. After the reaction is substantially complete, the excess amine isremoved by suitable means, as, for example by gentle warming. Ether isthen added to facilitate separation of the amine hydrohalide, which isthen removed from the reaction mixture by filtration. After the etherhas been removed by evaporation at room temperature, the unsaturatedhydrocarbon phosphonic diamide is separated from the residual mixture byconventional means, such as, for example, by fractional distillationunder reduced pressure. In some instances, a portion of the productpolymerizes during purification and a polymer remains in the reactor.Amines which are applicable are primary and secondary amines of theformula where R' is the same as heretofore defined. Although in generalprimary and secondary amines are applicable I prefer to use the primaryor secondary aromatic amines, such as aniline, N-methylaniline,2-aminoquinoline, 2- naphthylamine, diphenylamine, o-tolylamine; andsecondary aliphatic, carbocyclic, or heterocyclic amines, such asdiallylamine, dicyclohexenylamine, di-Z-butenylamine, dimethylamine,dicyclohexylamine, piperidine, and mor- Additional examples of aminesare allylamine, alpha-allylbenzylamine, bis-( p 2 butenylphenyl) amine,dicinnamylamine, and 4-phenylbutylamine. In some instances ammonia canbe used to produce the amide.

In my copending application, Serial No. 425,769, filed April 26, 1954,there are set forth, described and claimed certain haloalkenephosphonicdihalides and a method of preparation therefor. The haloalkenephosphonicdihalides of said application, which have a hydrogen atom attached tothe same carbon atom to which the phosphorus atom is attached, are amongthose suitable as starting materials for the preparation of phosphonicdiamides of this invention. As stated therein, the said dihalides arepreferably prepared by reacting the corresponding haloalkenephosphorustetrahalide with a carboxylic acid. Thus, 2-chloro- 3-butenephosphorustetrachloride, which is the preferred starting material, is reacted withacetic acid in accordance with the following equation:

As stated in the above referred to application when 1,3- butadiene isreacted with phosphorus pentachloride to form a chlorobutenephosphorustetrachloride three possible isomers can be obtained, i. e.,

+ CHaCOCl H01 At present it is believed that isomer No. 1, above,predominates. When a mixture of the said isomers is reacted with acarboxylic acid according to the above given equation a mixture of thecorresponding chlorobutenephosphonic dichlorides is obtained. Thus, whena mixture of the said chlorobutenephosphonic dichlorides is used as astarting material in the reaction with an unsaturated amine such asdiallylamine the corresponding alkadienephosphonic diamides areobtained, i. e.,

urated amine such as diallylamine the correspondingchloroalkadienephosphonic diamide is obtained, i. e.

N,N,N',N tetraallyl 2 chloro 1,3 butadiene 1- phosphonic diamide.

Where preferable, dehydrohalogenation involving a halogen atom attachedto a carbon atom can be accomplished by a separate step additional tothe amidation step, such as, for example, by treatment of ahaloalkenephosphonic diamide with alcoholic potassium hydroxide,powdered potassium hydroxide, powdered sodium hydroxide,2,6-dimethylpyridine or dimethylamine.

The products of this invention are valuable as plasticizers for a widerange of polymeric materials, including .aisn

. synthetic resins and syntheticrubber. They are also useful astextile-treating agents, and as monomers in the formation of polymersand copolymers. The polymers range from viscous liquids to brittleresins and rubbery solids.

Example I The isomeric N,N,N ,N' tetraallyl 1,3 butadienephosphonicdiamides were prepared by the following method:

To a solution of 107 g. (1.1 mol) of anhydrous diallylamine in 100 ml.of anhydrous ether, cooled to about -46 C., was added dropwise, withconstant stirring, 41.5

v g. (0.2 mol) of the chlorobutenephosphonic dichloride,

the preparation of which is described below (Example 11). When all ofthe phosphonic dichloride had been added, the flask was warmed gently toroom temperature, and the reaction was allowed to proceed withintermittent cooling to keep the temperature below 40 C., until, afterabout one hour, cessation of heat evolution indicated that the reactionhad proceeded substantially to completion.

The precipitate of amine hydrochloride was removed by filtration, washedwith ether, and dried. The ether was removed from the filtrate bydistillation, and 100 ml. of npentane was added to precipitate theremaining amine hydrochloride, which was removed by filtration. The

Example II The isomeric chlorobutenephosphonic dichlorides were preparedby the following procedure:

To a suspension of 454 g. of phosphorus pentachloride in 1200 cc. ofdried benzene was added, with constant stirring, 250 g. of butadiene.After standing at 15-20 C. overnight, 100 cc. (about 60 g.) of butadienewere added to replaceany butadiene that might have evaporated, and thesuspension was stirred for 8 hours. The next day, an additional 100 cc.of butadiene was added, and the suspension was stirred for two hours.After cooling the flask in an ice bath, 2.2 mols of glacial acetic acidwas added, while stripping off HCl, acetyl chloride, and some of thebenzene in vacuo. The remainder of the solvent was then removed in vacuofrom the resulting solution, and the residue distilled to yield 130 g.(33 percent) of chlorobutenephosphonic dichloride which boiled at 106 C.at 1.0 mm. Hg. It had the following characteristics: refractive index of1.5185 at 25 under white light; density of 1.436 at room temperature,and molecular refractivity, calculated, 42.05; found, 43.85.

A sample prepared by the procedure similar to the one described abovehad a chlorine content of 50.4 percent, as compared with a calculatedvalue of 51.2 percent.

Example III A 500 ml. flask equipped with dropping funnel, stirringunit, and reflux condenser was placed in a Dry Ice-acetone I reducedpressure.

amine hydrochloride was dried for 3 hours at.105 C..and

---then weighed. 72.9 grwere obtain'ed, a 91 percent theoret-ical yield."The'filtrate was strippedito 50. C., under 62.2 g. r of a red, veryviscous, jellylike oil remained. 1 When it was attempted to distill 61.1g. of this crude product at reducedpressure, 14.89, g. of diallylamineand 2.5 g. of a liquid boiling at 25, C., at

0.45 mm: Hg-were obtained asoverhead while polymerization occurred inthe flask to yield-43.3 g. of a dark plastic solid.

' Example IV Acsecond run was made forithe purpose of "preparing.additional isomeric;chlorobutenephosphonic dichlorides. 453 g.(2.17mol) .of-PCl 'was dissolvedin 1500 cc. of

vigorously refluxingwbenzene containediin a- 3-liter,' 3-

-necked flaskwhich was equipped with a reflux condenser and droppingfunnel. The flask was packed in ice, and cooled to below 40 C. 136. g.(2.52 mol) of butadiene dissolved in'300 cc. of benzene was then addedover a 25 minute period. The material, packed Jinice, "was then stirredfor 7 hours and allowed tostand overnight. To the pasty reaction masswas added dropwise, with constant stirring, 131 g. (2.18 mol) of aceticacid. The thick mixture turned clear, pale yellow. It was stripped withstirring to 25 C. at 20 mm. 'A dark tan oil, weighing 289.7 g.

(64.4 percent theoreticalyresulted. 'From 286.9 g. of thiscrudematerialwas obtained 184.5 g. (41.5 percent'theo- .retical) of afraction' boiling at 97-112 C. at 0.4 to 2.0

mm. Hg. It had arefractive index of 11 1.5186.

Example V The isomeric N,N,N,N'-tetrarnethyl-1,3-butadienephosphonicdiamides were prepared by the following method:

.warm to roomtemperature, and the excess dimethylamine was driven ofi bygentle heating. After adding 50 ccwof ether, the amine hydrochloride wasremoved by filtration, and washed with 100 cc. of ether. 46 g. ofdimethylamine hydrochloride was obtained. The ether was removed from thefiltrate, and the residue was distilled in vacuo to yield 21.5 g. ofisomeric N,N,N',N-tetramethyl-1,3-butadienephosphonic diamides, boilingat 102-120 C. at 1.25- 2.5 mm. The residue remaining in the distillationflask was a clear, amber resin.

A sample prepared by a method similar to the one described above gavethe following analysis:

Calculated for CaHmPONzZ C, 51.1; H, 9.11; P, 16.5.

Found: C, 50.1; H, 9.6; P, 15.9.

Example VI A second run was made for the purpose of preparing additionalisomeric N,N,N,N-tetramethyl-1,3-butadienephosphonic diamides. 100 g.(2.22 mol) of anhydrous dimethylamine was placed in a 500 cc. B-neckedflask, equipped with stirring unit, dropping funnel, and thermometer. Itwas cooled to -70 C. by means of a Dry Iceacetone bath, and then into itwas dropped slowly 42.5 g. (0.205 mol) of chlorobutenephosphonicdichloride which was prepared according to the procedure described abovein Example IV. During this addition the temperature was maintained at 70to 40 C. The amine hydrochloride separated readily. 50 cc. of ether wasadded. After two hours, the mixture was warmed gently. The precipitateof dimethylamine hydrochloride was filtered and washed well. 44.6 g.(88.8 percent theoretical) was obtained. The filtrate, which was a clearyellow oil, was stripped of ether, and then distilled under reducedpressure. 20.7 g. (53.7 percent theoretical) of a fraction boiling at116ll8 C. at 0.9 to 1.2 mm. Hg was obtained. lts refractive index was nl.5023.

In the above examples anhydrous conditions were employed. Whileanhydrous conditions are preferred less than anhydrous conditions can beemployed. Water reacts with the phosphonic dihalide causing it tohydrolyze, resulting in a lower yield. Otherwise, its presence is notharmful.

Although there is no reason to suspect that the structural formulasgiven as representing the compounds of the invention are incorrect,since said formulas were developed according to standard methods wellknown to those skilled in the art, the invention is not to be undulylimited by said formulas.

Obviously, one reading the above specification will realize that thevarious phosphonic diamides represented by the formulas given herein arenot necessarily equivalents in the usual sense of that term but ratherare alternatives each possessing different properties and, therefore,diiferent uses.

Reasonable variation and modification are possible within the scope ofthe foregoing disclosure and the appended claims to the invention, theessence of which is that: new compounds represented by the structuralformula N(R)z defined hereinabove have been provided, said new compoundsbeing phosphonic diamides characterized by either an alkapolyenegrouping, an alkenyne grouping, an alkapolyene grouuin or a five or sixmembered ring f rmed from one of said groupings, Formulas I, II, III,IV, V, and VI given herein being representative of said new com pounds;new compositions of matter comprising polymers of said phosphonicdiamides have been provided; and a method of preparing said phosphonicdiamides which comprises reacting a halophosphonic dichloride with anamine.

I claim:

1. A phosphonic diamide represented by the structural formula wherein: Ais a member selected from the group consisting of unsubstituted andhalogen-substituted alkapolyene, alkenyne and alkapolyyne hydrocarbonradicals, and a five to six membered ring, said ring having a skeletonconsisting of carbon atoms and having therein the carbon skeleton of oneof said hydrocarbon radicals; R is a member containing from zero to tencarbon atoms selected from the group consisting of hydrogen,hydrocarbon, and heterocyclic radicals, said hydrocarbon radicals beingselected from the group consisting of aromatic, saturated andunsaturated acyclic, and saturated and unsaturated alicyclic radicals,and combinations of the radicals as defined by R; and where, inaddition, two R' radicals together with the nitrogen atom attachedthereto can form a heterocyclic ring containing from five to sevenatoms, at least three of which are carbon, the remainder being selectedfrom the group consisting of carbon, nitrogen, sulfur and oxygen.

2. N,N,N,N tetramethyl 1,3 butadiene 1 phosphonic diamide.

3. N,N,N',N tetramethyl 1,3 butadiene 2 phosphonic diamide.

4. N,N,N',N' tetraallyl 1,3 butadiene 1 phosphonic diamide.

5. N,N,N,N tetraallyl 1,3 butadiene 2 phosphonic diamide.

6. A mixture of isomeric alkadienephosphonic diamides comprisingN,N,N',N' tetramethyl 1,3 butadiene 1- butadiene-Z-phosphonic diamide.

7. A mixture of isomeric alkadienephosphonic diamides comprisingN,N,N',N tetraallyl 1,3 butadiene 1- phosphonic diamide, and N,N,N',N'tetraallyl 1,3- butadiene-Z-phosphonic diamide.

8. Polymeric N,N,N',N' tetramethyl 1,3-butadienel-phosphonic diamide.

9. Polymeric N,N,N',N tetramethyl 1,3 butadiene- Z-phosphonic diamide.

10. Polymeric N,N,N',N' tetraallyl 1,3 butadienel-phosphonic diamide.

11. Polymeric N,N,N',N tetraallyl 1,3 butadiene- 2-phosphonic diamide.

12. A polymeric composition of matter comprising polymers of theisomeric mixture defined in claim 6.

13. A polymeric composition of matter comprising polymers of theisomeric mixture defined in claim 7.

14. The method of preparing a phosphonic diamide having a structuralformula as defined in claim 1 which comprises reacting ahaloalkenephosphonic dihalide with a compound selected from the groupconsisting of ammonia and an amine containing at least one hydrogen atomattached to the nitrogen atom.

15. The method of preparing a phosphonic diamide having a structuralformula as defined in claim 1 which comprises reacting ahaloalkenephosphonic dihalide with a compound selected from the groupconsisting of ammonia and an amine containing at least one hydrogen atomattached to the nitrogen atom to form a haloalkadienephosphonic diamidereaction product and reacting said product with a strong base.

16. The method of preparing a phosphonic diamide having a structuralformula as defined in claim 1 which comprises: adding ahaloalkenephosphonic dichloride to at least a stoichiometric quantity ofa compound selected from the group consisting of ammonia and an aminecontaining at least one hydrogen atom attached to the nitrogen atom,dissolved in a suitable inert solvent to form a reaction mixture,maintaining said reaction mixture at a temperature within the range of 0to C. during said addition, warming said reaction mixture, maintainingsaid reaction mixture within the range of 0 to C. until said reaction issubstantially complete as indicated by cessation of heat evolution,filtering said reaction mixture to obtain a precipitate and a filtrateand recovering said phosphonic diamide from said filtrate.

17. The method of claim 16 wherein said amine is diallylamine, saidhalophosphonic dichloride is chlorobutenephosphonic dichloride and saidalkapolyenephosphonic diamide is N,N,N,l tetraallyl 1,3butadienephosphonic diamide.

18. The method of claim 16 wherein said amine is dimethylamine, saidhalophosphonic dichloride is chlorobutenephosphonic dichloride and saidalkapolyenephosphonic diamide isN,N,N',N-tetramethyl-1,3-butadienephosphonic diamide.

19. The product of the reaction between diallylamine and achlorobutenephosphonic dichloride which has a boiling point ranging from157 to 170 C. at 1 mm. of Hg.

20. The product of the reaction between dimethylamine and achlorobutenephosphonic dichloride which has a boiling point ranging from102 to C., at 1.25 to 2.5 mm. Hg.

21. The product of the reaction between dimethylamine and achlorobutenephosphonic dichloride which has a boiling point ranging from116 to 118 C., at 0.9 to 1.2 mm. Hg.

References Cited in the file of this patent UNITED STATES PATENTS2,486,657 Kosolapoif Nov. 1, 1949 2,666,750 Dickey et a1 Jan. 19, 1954Patent No, 2,818,406

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION December 31, 1957James No Short It is hereby certified that error appears in the printedspecification of the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 2, line 33, for "and second occurrence read m when m Signed andsealed this 27th day of January 1959o (SEAL) Attest:

KARL Ho AXLINE Attesting Officer ROBERT C. WATSON Commissioner ofPatents

1. A PHOSPHONIC DIAMIDE REPRESENTED BY THE STRUCTURAL FORMULA